Process for solubilizing inorganic boric acid compounds in fuels and lubricating oils



United States Patent PROCESS FOR SOLUBILIZING INORGANIC BORIC ACID COMPOUNDS IN FUELS AND LUBRICAT- ING OILS James Hartley, Whitby, Wirral, England, and Ernest Colin Lumb, Amsterdam, Netherlands, assignors to Shell Oil Company, a corporation of Delaware No Drawing. Filed Dec. '19, 1957, Ser. No. 703,752

Claims priority, application Great Britain Dec. 21, 1956 16 Claims. (Cl. 252-18) This invention relates to a method for solubilizing boric acid and metal borates in liquid fuels used in internal combustion motors and in lubricating oils and greases. The invention provides a new and useful class of materials which, when present in the fuel used in a sparkignited internal combustion motor, reduce the amount of, and the adverse eflect of, deposits in the combustion chamber(s) of that motor, thus preventing or substantially reducing the increased fuel octane number requirement, and the abnormal fuel ignition characteristics which usually result from those deposits. The new materials provided by this invention also act as oxidation inhibitors and as detergents and impart extreme pressure resistance properties to lubricating oils and greases in which they are present.

According to this invention, compositions of matter comprising inorganic boric acid compounds of a kind which readily form stable, clear dispersions of those inorganic boric acid compounds in liquid fuels and in base stocks used in formulating lubricating oils and greases are prepared by hydrolyzing an organic ester of boric acid in the presence of a lyophilic ionic surface-active agent, a substantially non-polar organic liquid, and a water-miscible organic liquid, and, if desired, recovering from the resulting mixture a dispersible inorganic boric acid compound. Preferably, the non-polar organic liquid used is the fuel or the lubricant base stock in which it is desired to ultimately disperse the boric acid compound, and the dispersion of the boric acid compound in the fuel or lubricant base stock used is obtained directly by evapcrating from the final reaction mixture all of the material boiling below the fuel or lubricant base stock used. This lower-boiling material includes the water-miscible organic liquid, the alcohol resulting from hydrolysis of the organic borate, and any water which may be present in the mixture.

The products of this process contain substantial amounts of boron in a form readily dispersible in liquid fuels and lubricant base stocks to form stable, clear dispersions, containing up to by weight of the inorganic boric acid compound.

The new compositions of this invention are prepared by hydrolyzing an organic ester of boric acid in the presence of three materials:

(1) A lyophilic ionic surface-active agent; (2) A substantially non-polar organic liquid; (3) A substantially water-miscible organic liquid.

The dispersible boron-containing product of this process is a complex of an inorganic boric acid compound with the oleophilic ionic surface-active agent.

By the term inorganic boric acid compound is meant all acidic compounds derived from reaction of boron tnoxide with varying amounts of water, and the metal salts of those acidic compounds. Of the free acids, the most important is boric acid itself (i.e., orthoboric acid, H 30 Tetraboric acid, 11 E 0 and metaboric acid, H30 also are included, these acids normally being present in the form of their metal salts. As will be evident from the discussion hereinafter of the way in which the inorganic boric acid compound is prepared, the metal salts of the inorganic boric acids may be the salts of any metal, but the alkali metal salts and the alkaline earth metal salts of the inorganic boric acids are preferred.

Preparation of the inorganic boric acid compound is eifected by hydrolysis of an organic ester of boric acid or, equivalently, an organic borate. The hydrolysis is effected by contacting the organic borate with water-in which case, the resulting inorganic boric acid compound is orthoboric acid itselfor with a metal base or an aqueous solution or suspension of a metal base-in which case, the resulting inorganic boric acid compound is the salt of an inorganic boric acid and the metal of the metal base. As used herein, therefore, the term hydrolysis means the conversion of the organic borate to the inorganic boric acid compound, whether the hydrolysis be elfected by water or by a metal base, and whether or not the hydrolysis is accompanied by salt formation.

As the organic ester of boric acid, there may be used any ester of boric acid (which term includes both orthoboric acid and metaboric acid)any organic boratewhich readily reacts with water to form a free boric acid and the corresponding alcohol of the ester group, or which reacts with a metal base to form the corresponding metal borate and the corresponding alcohol of the ester group. It is preferred that the organic borate be such that the alcohol formed on hydrolysis of the borate either boils below C. or forms an azeotrope with water which boils below 100 C. at atmospheric pressure. The suitable organic borates include the monoesters, the diesters and the triesters of orthoboric acid, and the monoesters of metaboric acid. In the diand triesters, the ester groups may be the same, or they may be different, and each may be of straight-chain, branched chain or cyclic configuration. The preferred organic borates are those which are readily soluble in liquid hydrocarbons. As is pointed out at pages 971 and 982-3 of the article by M. F, Lappert, entitled Organic Compounds of Boron, in volume 56 of Chemical Reviews, organic orthoborates and metaborates generally hydrolyze readily. The alkyl orthoborates, particularly those wherein each alkyl group is a lower alkyl group (i.e., containing up to 10 carbon atoms), are preferred, and of this group the trialkyl orthoborates in which each alkyl group contains from 1 to 6 carbon atoms are most desirable because of the ease it is preferred that the borate ester be so chosen that the alcohol resulting from hydrolysis of the organic borate is the same as the lower alkanol used as the water-miscible liquid.

The amount of water used to efiect the hydrolysis of the organic borate should be at least the amount theoretically required to convert all of that borate to the corresponding boric acid. Generally, it will be found desirable to use a small to moderate excess-for example, up to about three times the theoretical, or 200% excessof water, to insure complete hydrolysis of the organic borate. The amount of water added to the reaction mixture is at least the amount required to join an azeotrope with the water-miscible organic liquid added to the reaction mixture, plus the alcohol formed by hydrolysis of the organic borate. Preferably, there is used a moderate excess-up to 100% excessof water over the minimum required to form the azeotrope. Any water remaining after all of the azeotrope is removed then is removed by distillation. Where the hydrolysis is effected by a metal base, the amount of metal base used should be at least the amount theoretically required .to convert all of-theboric acid produced by the hydrolysis to the corresponding metal salt--which' saltmay be the partial or acid salt of boric acid wherein but one or two of the acidic groups of boric acid are reacted with the metal base. A small excess over this amount may be found desirable to insure complete reaction of the boric acid with the metal base. In general, it is preferred to use as small an excess of metal base as is found necessary to insure completion of the desired reaction, since any excess of metal base must be recovered from the final reaction mixture by the use of settling, filtration or centrifuging of that mixture. Where the hydrolysis of the organic borate is effected by an aqueous solution or suspension of a metal base, the amount of water in that solution or suspension will be governed not only by the factors considered hereinbefore, but also by the desired concentration of metal base in the solution or suspension. Preferably the metal base amounts to from about to about 60% of the weight of the solution or suspension. Where the hydrolysis of the organic borate is effected by a metal base, it is preferred that the substantially anhydrous metal base be used. 7

As the metal base, there may be used any base-that is, any hydroxide or basic oxide-of any metal, including monov-alentand polyvalent-metals. Preferred metal bases are the hydroxides of (a) the metals of group II of the periodic chart of the elements (Merck and (30., Revised, 1955)-i.e., the alkaline metalsand particularly the members of this group having an atomic number of from 12 to 56--i.e., magnesium, strontium, calcium and barium, and (b) the alkali metals-Le, the members of group IA of the periodic chart of the elements (Merck and Co., Revised, 1955). The hydroxides of the three lower molecular weight members of this classlithium, sodium and potassium-are particularly desirable because of their wide availability and low co'st.

As the necessary surface-active agent there can be used any lyophilic ionic surface-active agent. The term lyophilic is intended to have its usual meaning in this artthat is, it is synonymous with hydrophobic and defines a compound which is substantially insoluble in and immiscible with water, and which is readily soluble in organic liquids having electric dipole moments of 0.5 Debye units or less. This class of surface-active agents also is known in the art as non-aqueous surface-active agents. Schwartz and Perry, Surface Active Agents, Interscience, 1949, at page 485. Of particular interest are those commonly known in the art as lubricating oil detergents (Schwartz and Perry, supra, page 487).

Of the non-aqueous surface-active agents, of particular interest are:

(1) The lyophilic anionic surface-active agents, typified by the oil-soluble salts of organic acids containing at'least 8'carbon atoms per molecule and the oil-soluble salts of phenolic compounds containing at least 8 carbon atoms per molecule;

(2) The lyophilic cationic surface-active agents, typified by the organic amino compounds and quaternary ammonium compounds containing at least 8 carbon atoms per molecule. 7

An excellent summary of typical suitable oil-soluble salts of organic acids is set out in United States Patent No. 2,777,874, issued January 15, 1957. To be concise, the said survey is hereby incorporated herein and is to be considered as forming a part of the disclosures of this specification. The suitable'salts of oil-soluble organic acids include both metal salts and organic salts. The metal salts include the mono or polyvalent metals, such as the light or heavy metals, or the alkali and alkaline earth metals such as sodium, lithium, potassium, calcium, barium, strontium, magnesium. Other specific examples, are zinc, cadmium, mercury, lead, tin, iron, cobalt, copper, manganese, aluminum, chromium, nickel, etc. The organic salts include those formed with ammonia and substituted ammonias, such as mono-, di-, and tri-ethanolamines; ethyl-, propyl-, butyl-, and amyl-amirtes, e tc.,

4 pipcridine, pyridine, etc. The preferred salts are the salts of the metals of group II of the periodic chart of the elements (Merck and (30., Revised, 1955)-i.e., the alkaline earth metals-and particularly the members of this group having an atomic number of from 12 to 56 i.e., magnesium, strontium, calcium and barium.

Particularly preferred are the metal salts of the oilsoluble carbocyclic acids, including those containing a benzenoid structure and those containing a cycloaliphatic structure. Preferred are the salts of the carbocyclic carboxylic acids and the carbocyclic sulfonic acids.

Salts of the carbocyclic carboxylic acids include, for example, the salts of alkyl-substituted aromatic carboxylic acids, including the alkyl-substituted hydroxyaromatic carboxylic acids (salicylic acids), and the cycloaliphatic carboxylic acids, particularly the naphthenic acids.

Salts of the alkyl-substituted aromatic carboxylic acids containing at least about 10 carbon atoms in the substituent groups are particularly desirable. Salts of both the mononuclear -acids'i.e., those acids which may be considered to have been derived from benzene-and polynuclear acidsthose which may be considered to have been derived from naphthalene-arc included. Of this class, the most widely available are the salts of alkylsubstituted hydroxyaromatic carboxylic acids-the salicylic acids-in which the alkyl group or groups are longchain in structure and contain a total of at least about 12 carbon atoms. The most desirable class of these salicylic acid salts comprises those which have been derived from benzene or phenol which has been alkylated with straight-chain hydrocarbons containing from about 8 to about 26, and preferably from about 10 to about 22, carbon atoms. Salts of alkyl-substituted salicylic acids of the kinds prepared by the processes disclosed in United States Patent No. 2,807,643 are preferred members of this class of oil-soluble carbocyclic carboxylic acids.

The references herein to salts of alkyl salicylic acids are intended to cover salts of the individual acids and also salts of mixtures of such acids having difierent alkyl substituents, for example, salts of a mixture of alltyl salicylic acids having alkyl groups containing from about 10 to about 22 carbon atomssuch as a mixture of C -C monoand di-alkyl salicylic acids. Salts of technical grades of such acidsi.e., mixtures of such acids normally containing some of the corresponding phenates and phenols, will generally be used in practice and in many cases are to be preferred.

Salts of oil-soluble cycloaliphatic carboxylic acids containing at least about 12 carbon atoms are particularly suitable examples of this class being the petroleum naphthenic acids, cetylcyclohexane carboxylic acids, di-lanryl decahydronaphthalene carboxylic acids, di-octyl-cyclopentane carboxylic acids, and the like. Of particular interest, because of their wide availability at low cost, are salts of the petroleum naphthenic acids, that is, monobasic carboxylic acids of the general formula, RCOOH, wherein R is the naphthenic radical (a radical predomi nantly derived from cyclopentane or a homolog of cyclepentane). The carboxyl group of the petroleum naphthenic acids normally is attached to a side chain of the naphthenic group, so that the petroleum naphthenic acids normally have the stmcturer V V (IJHQ-CHQ a r V The nature of the petroleum naphthenic acids, as well as suitable individual acids and mixtures ofsuitable acids, is set out in detail in Kirk-Othmer, Encyclopedia of Chemical Technology, Interscience Encyclopedia Co., 1952, volume 9, in the section thereof entitled Naphthenic Acids, pages 241, 247.

Salts of various oil-soluble carbocyclic sulfur acids also are suitable, including the carbocyclic sulfonic acids, sulfamic acids, sulfinic acids, thiosulfonic acids, and the or may not be alkylated; and the like.

like. These acids can be of either cycloaliphatie or alkylsubstituted aromatic (including both mononuclear and polynuclear aromatic) configuration.

A particularly desirable group of oil-soluble salts of carbocyclic sulfur acids comprises the salts of sulfonic acids of various types, including cycloaliphatic, hydroaromatic, aromatic (including both benzenesulfonic acids and naphthalene sulfonic acids) and heterocyclic acids, and acids of mixed types. Examples of salts of suitable acids include the salts of sulfonic acids of alkylated aromatic hydrocarbons, such as benzenesulfonic acids, toluene sulfonic acids, naphthalene sulfonic acids, triisopropylnaphthalene sulfonic acids, polyamylnaphthalene sulfonic acids, diphenyl sulfonic acids and the like. Salts of sulfonic acids of aromatic hydrocarbons substituted by a higher alkyl group or groups and in which the alkyl substituent group or groups contain a total of at least about 8, but preferably not more than about 18, carbon atoms, are of particular interest. Salts of sulfonic acids of phenols, which can be monocyclic as well as polycyclic, monohydric as well as polyhydric, and which preferably also contain alkyl and/ or aryl substituent groups are also suitable. Examples of this class of salts include the oilsoluble salts of cresol sulfonic acids, xylenol sulfonic acids, naphthol sulfonic acids, catechol sulfonic acids and the like. Salts of sulfonic acids of completely or partly hydrogenated aromatic compounds, for example, tetrahydronaphthalene sulfonic acid, are also suitable. Particularly preferred, however, because of their wide availability, are salts of the petroleum sulfonic acids, particularly the petroleum sulfonic acids which are obtained by sulfonating various hydrocarbon fractions, such as lubricating oil fractions and extracts rich in aromatics which are obtained by extracting a hydrocarbon oil with a selective solvent, which extracts may, if desired, be alkylated before sulfonation by reacting them with olefins or alkyl chlorides by means of an alkylation catalyst; organic polysulfonic acids such as benzene disulfonic acid, which may The preferred salts for use in the present invention are those of alkylated aromatic sulfonic acids in which the alkyl radical(s) contain at least about 8 carbon atoms, for example, from about 8 to about 22 carbon atoms, exemplary members of this preferred group of sulfonate starting materials .being the aliphatic-substituted cyclic sulfonic acids in 'which the aliphatic substituent(s) contain a total of at least 12 carbon atoms, such as the alkyl aryl sulfonic acids, alkyl cycloaliphatic sulfonic acids and alkyl-heterocyclic sulfonic acids and aliphatic sulfonic acids in which the aliphatic radical(s) contains at least 12 carbon atoms.

Specific examples of these oil-soluble sulfonic acids include: petroleum sulfonic acids, petrolatum sulfonic acids, monoand polywax-substituted naphthalene sulfonic acids, substituted sulfonic acids, such as cetyl-chlorobenzene sulfonic acids, cetylphenol sulfonic acids, and the like, aliphatic sulfonic acids, such as paraflin wax sulfonic acids, unsaturated parafiin wax sulfonic acids, hydroxysubstituted parafiin Wax sulfonic acids, chlor-substituted wax sulfonic acids, etc.; cyclo-aliphatic sulfonic acids, such as petroleum naphthalene sulfouic acids, cetyl-cyclopentyl sulfonic acids, monoand polywax-substituted cyclohexyl sulfonic acids and the like.

The term petroleum sulfonic acids is intended to cover all sulfonic acids which are derived directly from petroleum products.

The metal salts of these acids may be prepared by directly reacting the acid with a metal base or a metal salt. Alternatively, the polyvalent metal salt may be prepared by first forming the alkali metal salt of the acid, by neutralizing the acid with an alkali metal base, and then converting the alkali metal salt to the polyvalent metal salt by the metathetical reaction of the alkali metal saltwith a polyvalent metal salt or base. Methods for preparing the polyvalent metal salts by all of thesemethods are well known in the art.

0f the salts of phenolic compounds, the metal-salts of polyhydroxy phenolic compounds containing atleast 8 carbon atoms per molecule are preferred. These polyhydroxy compounds are prepared by the condensation of a low molecular weight carbonylic compoundi.e., a low molecular weight aldehyde or ketone-with an oil-soluble alkyl phenol. The carbonylic reactant is an aldehyde or ketone containing not more than about 5 carbon atoms per molecule-for example, formaldehyde, acetaldehyde, acetone, methyl ethyl ketone, crotonaldehyde, butyraldehyde, diethyl ketone, and the like. The condensation products of formaldehyde are preferred.

The phenol reactant must be oil-s0luble.-that is, it must contain at least one hydrocarbon group attached directly to the aromatic ring, said hydrocarbon group or groups having sufiicient carbon atoms to make the phenol soluble in mineral oils, yet not so many carbon atoms as to make the phenol or the condensation products derived therefrom heavy, oil-insoluble materials. Suitable phenols contain at least one hydrocarbon group containing at least 4 carbon atoms, and it is preferred that the hydrocarbon group contain from about 6 to about 12 carbon atoms. The total number of carbon atoms in the substituent hydrocarbon group or groups should not exceed about twenty-five. The phenol must have an available ortho position-i.e., an unsubstituted position ortho to the hydroxyl radical; preferably the solubilizing hydrocarbon group is located at the 4position on the ring, and where there are two such alkyl groups, they preferably are located at the 2- and 4-positions of the ring. The solubilizing radical preferably is an alkyl group, but cycloalkyl or aryl groups are also satisfactory. Typical solubilizing groups are: butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, lauryl, stearyl, oleyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, propylcyclohexyl, dicyclohexyl, methylated dicyclohexyl, benzyl, ethylphenyl groups and the like. The aromatic nucleus, as well as the attached hydrocarbon radicals, may also contain other reactive groups, such as halogen groups. The aromatic nucleus may be monoor di-cyclic, resulting in such nuclei as naphthalene, tetraline, diphenyl, etc.

The carbonylic compound is condensed with the phenol at the ortho position by methods known to the art-for example, by heating the mixture of phenol and carbonylic compound with an acid or basic catalyst-whereby a resinous condensation product containing a plurality of hydroxyl groups is obtained. Depending upon starting materials and condensation conditions, the products may vary in appearance from viscous liquids to more or less brittle solids which may or may not be crystallized. A number of such resinous condensation products are commercially available, and since their methodsof manufacture are generally known, further details regarding such manufacture will not be set out here. Suitable oilsoluble condensation products of this kind have a molecular weight under 1000, most desirably about 800 to about 1000.

The condensation product is converted into the metal derivative by treating the condensation product with the appropriate metal hydroxide, or by methathetic conversion of a different metal derivative of the condensation product. Such metalderivatives and methods for preparing them are well known in the art. United States Patent No. 2,250,188 described in detail the preparation pf various condensation products of phenols with formaldehyde and various metal derivatives thereof. These salts are preferredfor use in the process of this invention. 1

The principal lyophilic cationic surface acti ve agents are the organic amine compounds and quaternaryammonium compounds. The organic amino compounds which can be used in the process of-the invention include the oil-soluble primary, secondary or tertiary aliphatic or cycloaliphatic amines or the N-acyl derivatives of such amines, containing at least 8, and preferably not more than 24, carbon atoms in the molecule, "Typical of these amines are the saturated primary amines having a carbon chain of 16-22 carbon atoms, such as l-hexadecylamine, l octadecylamine, palmitylamine, stearylamine, arachnidylamine, behenylamine and the like; primary monounsaturated amines, such as oleylamine, palmitoleylamine, petroselinylamine, vaccenylamine, gadoleylamine, cet oleylamine, erucylamine and the like; di-unsaturated amines containing at least one carbon chain of 16-22 carbon atoms, such as linoleylamine; tri-unsaturated amines, such as linolenylamine, licanylamine, eleostearylamine and the like, and secondary and tertiary amines containing at least one carbon chain of from 16-22 carbon atoms. Diamines, triamines and other types of amines having at least one carbon chain of 16-22 carbon atoms likewise are suitable. Certain of these long chain amines are commercially manufactured by Armour and Company, Chicago, Illinois, under the generic trade names Armeen and Duomeen. Specific amines of this type are (compositions are expressed on a weight basis):

Primary amines- Armeen SD, 20% hexadecylamine, 17% octadecylamine, 26% oc-tadecenylamine, 37% octadecadienylamine;

Armeen CD, 8% octylamine, 9% decylamine, 47% dodecylamine, 18% tetradecylamine, 8% hexadecylamine, octadecylamine, 5% octadecenylamine;

Armeen l2, 2% decylamine, 95% dodecylamine, 3% octadecenylamine;

Armeen HTD, 2% decylamine, 95% dodecylamine, 3% tetradecylamine;

Secondary amines- Armeen 2C, 8% dioctylamine, 9% didecylamine, 47% didodecylamine, 18% ditetradecylamine, 8% dihexadecylamine, dioctadecylamine;

Armeen 2HT, 24% dihexadecylamine, 75% dioctadecylamine, 1% dioctadecenylamine.

Polyamines- Duomeen T, mixture of N-alkyl trimethylene diamines of the formula Heterocyclic amines, such as pyridine and pyrimidine derivatives also are suitable. An especially preferred type of-heterocyclic amines comprises those included in the tetrahydropyrimidine nucleus and particularly those having at least 10 carbon atoms per molecule. Such materials include alkylated l,2,3,4-tetrahydropyrimidines,

2,3,4,5 tetrahydropyrimidines and 3,4,5,6 tetrahydropyrimidines. A typical member of this species is 2-heptadecyl and 3,4,6-trimethyl, 3,4,5,6-tetrahydropyrirnicline. Other suitable materials are the following: 2-dodecyl, 4,4,6-trimethyl, 3,4,5,6-tetrahydropyrimidine; 2,4-dimethyl, 2,4,6-trioctyl, 2,3,4,5-tetrahydropyridimine; 6heptadecyl l,2,3,4-tetrahydropyrimidine.

Another class of suitable lyophilic ionic surface-active agents may be generically described as hydroxyalkyl polyalkylene amines. These are preferably in the form of amido-amines in which at least of the amino nitrogen atoms are in the amino form with relatively high molecular Weight organic acids. Other materials include polyalkyl amines, aliphatic hydroxy amines and amido alkyl amines. Suitble polyalkylene polyamines include such substances as triethylene tetramine and tetraethylene pentamine.

Suitable lyophilic derivatives are those in which a hydroxyalkyl group is attached to a nitrogen atom, such as hydroxyethyl ethylenediamine or those in which the hydroxy radical is'a substituent attached to a hydro carbon chain separating two nitrogen atoms. Such a material is: 2-hydroxy-1,3-diaminopropane.

An especially desirable type of amine compound comprises the complex mixtures of amines obtained by condensation of a monohaloepoxyalkane with ammonia or a low molecular weight aliphatic amine. The preferred type of material within this class includes the condensation products of epichlorohydrin and ammonia. Generally, these materials are prepared by heating the ammonia or amine with the monohaloepoxyalkane at a temperature between about 20 C. for a period between about 10 minutes and about 4 hours. Preferably, the ammonia or amine is present in a ratio of between about 4 and about 20 moles per mole of monohaloepoxyalkane.

Under these reaction conditions a mixture of derivatives is formed. Ordinarily, the reaction product comprises from 5% to of 1,3-diamino 2-hydroxypropane with minor amounts each of dimeric and polymeric derivatives. The exact configuration of these dimers and polymers has not been determined. It is believed that they are for the most part linear in structure and may be linked through either the nitrogen atoms, or through hydroxyl groups to form ether type dimers or polymers. The dimer is believed to have the following structure:

The above types of materials may be utilized without amide formation if they are lyophilic in nature. However, in many cases, it is preferable to cause amide formation to take place with high molecular weight organic acids in order to produce amido amines having especially suitable properties for use in the process of this invention. Preferably, the acids employed are higher fatty acids having at least 12 carbon atoms and generally are derived from mixtures of naturally occurring materials such as animal and vegetable fats and oils. Similar results are obtained by partial amide formation with still more complicated mixtures, such as the crude mixture of acids known as tall oil. The most efiective type of such mixture comprises those mixtures having a preponderance of fatty acids containing from 14 to 20 carbon atoms and preferably from 16 to 18 carbon atoms.

The partial amides especially suitable for use in this invention may be obtained by heating the amines, such as the condensation product of epichlorohydrin and ammonia, to a temperature between about and 225 C. for a period between about 15 minutes and 2 hours. Under these circumstances, the amides so formed comprise from about one-third to about two-thirds of the nitrogen atoms present in the amine molecule. The precise nature of these compounds and details of their preparation are set out in U.S. Patent 2,623,852, issued December 30, 1952, the pertinent portions of which are hereby incorporated into and made a part of this disclosure.

The quaternary ammonium compounds which can be used in the process of the invention are those containing at least one and preferably two aliphatic hydrocarbon radicals of 8 or more carbon atoms, such as trimethyl octadecyl ammonium chloride, trimethyl octadecadienyl ammonium chloride, trimethyl hexadecyl ammonium chloride, trimethyl tetradecyl ammonium chloride, trimethyl octadecenyl ammonium chloride, dimethyl dioctadecyl ammonium chloride, dimethyl dihexadecyl ammonium chloride, dim ethyl ditetradecyl ammonium chloride, dimethyl octadecyl octadecenyl ammonium chloride, dimethyl octadecenyl octadecadienyl ammonium chloride, diethyl dihexadecyl ammonium chloride and ethyl propyl dioctadecyl ammonium chloride. Other compounds which may be used in the process of the invention are the quaternary pyridinium compounds containing an aliphatic radical of 8 or more carbon atoms such as lauryl pyridinium chloride, cetyl pyridinium alkanes, such as heptane, octane,

chloride and octadecyl pyridinium chloride. While/the quaternary ammonium chlorides have been exemplified above the corresponding bromides, acetates or hydroxides may be employed. It will be further understood that the short chain radicals present in each of the above-designated quaternary smts are more or less immaterial, but may be preferably aliphatic radicals having from 1 to 7 carbon atoms. Mixtures of these quaternary ammonium compounds may also be used. Commercially available quaternary salts of the above variety are usually materials wherein the long chain radicals have from 12 to 18 carbon atoms each.

As the substantially non-polar organic liquid there may be used an organic liquid which has an electric dipole moment not greater than that exhibited by branchedchain hydrocarbons-Le, an electric dipole moment less than about 0.5 Debye unit. It is preferred that the electric dipole moment of the liquid be 0.0. By the term Debye unit is meant that measurement of electric dipole moment normally given this name. One Debye unit it defined to equal 1X10 electrostatic units. As used in this specification, the term electric dipole moment has its usual meaninge.g., it is a description or measure of the magnitude of the dipole electrostatic field existing in a given organic compound, the magnitude of the moment being the product of either of the two (opposite) electrostatic charges and the distance between those charges. Further, the term electric dipole moment is herein used to mean the electric dipole momentof a compound or solution at ordinary temperatures-cg, about 20 to C. The value(s) of such dipole moment(s) for organic compounds in the pure form or in representative solvent are given in such compilations of physical data as Tables of Electric Dipole Moments, compiled by L. G. Wesson, The Technology Press (1948). These liquids normally are substantially immiscible with water. Included among the suitable liquids are the normally liquid hydrocarbons,

which term includes those liquids which are referred to herein as liquid fuels, mainly liquid hydrocarbons boiling in the gasoline, kerosene or fuel oil ranges. Also included among the suitable liquids are those which are referred to herein as lubricating oils, mainly mixtures of liquid hydrocarbons obtained from petroleum and boiling in the lubricating oil ranges, but also including synthetic lubricating oils of suitable low dipole moment, such'as the dialkyl esters of long chain aliphatic dicarboxylic acids and the polyoxyalkylene liquids. Individual compounds, both aromatic (such as benzene, toluene, the xylenes) and aliphatic (such as the normally liquid and the like), including both straight-chain and branched-chain configurations, and mixtures of such compounds are suitable. The normally liquid hydrocarbons, including those boiling as low as the gasolines, and those boiling as high as the lubricating oils, are preferred.

As the necessary water-misible organic liquid, there may be used any non-acidic-i.e., neutral 'to basic, organic liquid which is substantially miscible with water and it is preferred that the organic liquid be completely miscible with water. By substantially water-miscible organic liquid is meant organic liquids which are capable of forming homogeneous mixtures with up to about 10% by volume of water in addition to those organic liquids which are miscible with water in higher proportions, for example at least 50% by volume. Organic liquids which are miscible with water in all proportions are, however, preferred. Suitable organic liquids include such compounds as alcohols, ketones, alkyl esters of lower monocarboxylic acids, ethers, including heterocyclic others such as the dioxanes, and amides, such as dimethyl formamide. The preferred organic liquids are the oxygen-containing organic liquids having an electric dipole moment (as that term has hereinbefore been defined) of at least about 1.0 Debye unit and which boil below the initial boiling point of the non-polar organic liquid and preferably should either boil below C. or form an azeotrope with water which boils below 100 C. at atmospheric pressure. It is preferred that the oxygen-containing organic liquid be aliphatic in character, which includes also the cycle-aliphatic compounds, the aliphatic alcohols, the aliphatic ketones, such as methyl ethyl ketone, diethyl ketone, methyl propyl ketone and cyclohexanone; the aliphatic others, such as diisopropyl ether, methyl and ethyl cellusolves and the like, and esters of aliphatic carboxylic acids, such as ethyl acetate, ethyl lactate, ethyl propionate, and nand isopropyl acetates. A preferred class of the oxygen-containing organic liquids comprises the monohydric lower aliphatic alcohols, particularly those containing from 1 to about 6 carbon atoms. Examples of this class include methanol, ethanol, land 2-propanols, n-, sec-, and tert-butyl alcohols, and the various C and C -alcohols, both straight-chain and branchedchain in configuration. Since it is preferred that the oxygen-containing organic liquid be completely watermiscible, the alkanols containing from 1 to 4 carbon atoms are most desirable. In general, optimum utilization of the boron present in the reaction zone appears to be obtained where isopropyl alcohol or the C alkanols,

particularly nand iso-butyl alcohols are used.

According to this invention, the new dispersi'ble inorganic boric acid compounds are prepared by mixing the surface-active agent, the non-polar organic liquid, the water-miscible organic liquid and the organic borate and adding the water or metal base to the mixture to hydrolyze the borate. The inorganic boric acid compound is dispersed in the non-polar liquid. Recovery of that dispersion preferably is accomplished by removing by vaporization all of the crude reaction mixture which boils below the boiling temperature of the non-polar organic liquid. If any excess of metal base was used in the hydrolysis of the organic ester of boric acid, that excess may be removed by filtration, decantation, centrifugation or like treatment of the dispersion. Where the nonpolar organic liquid used is the liquid fuel or the lubricant stock in which the dispersible inorganic boric acid compound ultimately is to be dispersed, no further treatment of the product dispersion is required, other than dilution thereof to give the desired concentration of boron. Where the non-polar liquid used is not the liquid in which the dispersible inorganic boron compound is ultimately to be dispersed, the dispersible inorganic boron compound can be recovered by distillation of the non-polar organic liquid. Alternatively, where the non-polar organic liquid used is a light hydrocarbon, and the inorganic boron compound is to be dispersed in a lubricant stock, recovery of the inorganic boron compound and dispersion thereof in the lubricant stock is most conveniently eflected by mixing the stock with the dispersion of the inorganic boron compound in the non-polar organic liquid, and then distill off the non-polar organic liquid to give directly a dispersion of the inorganic boric acid compound in the lubricant stock.

The concentration of the surface-active agent in the non-polar organic liquid is not critical-the primary requirement is that suflicient of the non-polar liquid be used to completely dissolve the surface-active agent and to provide a readily fluid solution. The concentration ofthe surface-active agent in the non-polar liquid should, however, be at least about 5% by weight (based on the sum of the weights ofthe surface-active agent and the nonpolar liquid) to provide reasonable reaction rates.

The Weight aratio between the organic borate and the surface-active agent may be varied within wide limits, but is preferably within the range of 1:10 and 1:1.

The amount of water-miscible liquid used should comprise at least about 5% by weight, and preferably 10% by weight of the total liquid present in the reactionzone--i.e., the sum of the Weights of the non-polar liquid and the water-miscible liquid. It is preferred that the:

a ents 1 I amount of water-miscible liquid be at least about 20% of the total weight of liquid present in the reaction mixture.

C. are seldom necessary. Reasonable reaction rates nor mally are obtained fromabout ordinary room temperature (i.e., about 20 C.) to about 120 C.

The reaction may be carried out at any pressure, including atmospheric pressure. The pressure should be sufiicient to maintain the volatile components of the reaction mixture in the liquid phase.

The reaction time is not a critical factor in the process of the invention. In general, hydrolysis of the organic borate and solubilization of the resulting inorganic boric acid compound requires but a few minutesin some cases as little as 5 to minutes is entirely adequate. In most cases, a somewhat longer reaction time-of the order of to 30 minutesis desirable to insure complete reaction. Seldom will a reaction time of more than about 4-5 hours he required, and generally no more than 2 hours reaction time is necessary.

It will be evident from the foregoing description of the process of the invention that it is not always necessary to use as starting material a pure organic borate, since it is also possible to prepare that borate in situ from boric acid and the corresponding alcohol. This may be done to particular advantage where the alcohol used in preparing the borate also is the water-miscible organic liquid. For example, trimethyl borate can easily be prepared in situ by stirring together boric acid and an excess of methanol. The solution of trimethyl borate in methanol thus obtained can then be mixed with a solution of the surfaceactive agent in the oil. proportion of water, the methanol preferably is then removed by distillation, whereby a clear dispersion of the boric acid in the oil is obtained.

By means of the process of the invention it is possible to prepare dispersions of a boric acid and alkali metal and alkaline earth metal borates containing up to 10% of the boron compound. Usually, however, the dispersions contain between 0.2 and 6% of the boron compound. While normally the product dispersions resulting from performance of the process of the invention are quite stable, infrequently it may be found that where the product contains a high concentration of the inorganic boric acid compound the product dispersion is slightly unstable, and a part of the solubilized inorganic boric acid compound precipitates. This is easily prevented by permitting a small amount of the water-soluble organic liquid to remain in the dispersion, or by adding a small amount of the water-soluble organic liquid to the dispersion. gTo preclude precipitation of any of the solubilized inorganic boric acid compound when the Water-miscible organic liquid is removed, and where the water-miscible organic liquid is a low-boiling compound, such as a lower alcohol or ketone, a less volatile water-miscible organic liquid may be added and the low-boiling liquid removed by distillation. For this purpose, very suitable higher boiling water-miscible organic liquids are the branched-chain aliphatic alcohols containing at least 6 carbon atoms per molecule, such as Z-ethylhexanol. For this purpose, the.

amount of'water-miscible organic liquid which is allowed to remain, or which is added, need not be large. Usually, 7

about 0.5% by weight of water-miscible organic liquid based on the weight of thedispersion, is suflicient, and

seldom will an amountin excess of about 5% of. theweight of the dispersion be'reqiiiredi The process of the invention can be carried out at any After addition of the required constitutes a general description of the process of the invention. The following examples showing application of that process in particular instances are included as illustrations of the use of that process. These examples are intended only to illustrate the invention, and are not intended to limit that invention in any way. In these examples, the abbreviations p.b.w. and p.b.v. mean parts by weight and parts by volume, respectively, and the relationship between parts by weight and parts by volume is the same as that which exists between the kilogram and the liter.

EXAMPLE I EXAMPLE II A solution of trimethyl borate was prepared by dissolving boric acid 18 p.b.w. in methanol 95 p.b.w. and this solution was added dropwise with stirring to a mixture of 94.8 p.b.w. of calcium naphthenate, 22 p.b.w. of

lime and 500 p.b.w of xylene which had previously been stirred for 15 minutes at 50 C. The actual mixture was stirred continuously for 2 hoursat 50 C. and the methanol and some xylene removed by distillation under slightly reduced pressure. The residue was filtered to give a clear solution (510 p.b.w.) which contained 0.57% of boron present as calcium borate.

EXAMPLE III A solution was prepared by 24.5 p.b.w. ct trimethyl borate and 24.4 p.b.w. o-t Armeen CD in a mixture of 500 p.b.v. of xylene and p.b.v. of methanol. The trimethyl borate was hydrolyzed by the addition of 18.9 p.b.w. of water and 100 p.b.v. of methanol. Subsequently, the mixture was distilled until a temperature of about 70 C. was reached, at which the distillation was interrupted and 4 p.b.v. of 2-ethylhexano1 were added. The.

distillation was then resumed until the methanol was completely removed, resulting in a dispersion of boric acid in xylene containing 2.75 by weight of boric acid.

EXAMPLE IV p.b.w. of boric acid with 1024 p.b.v. of methanol until dissolved. The above-described xylene solution containing 465 p.b.w. of calcium naphthenate was then added followed by the addition with vigorous stirring of a mixture of 50 p.b.v. of water and 800 p.b.v. of methanol.

The water andmethanol were removed by distillation in vacuo and the residue filtered hot'to give 2 800 p.b.w. of a clear brown liquid containing 2.6% by weight of boric acid. l v

EXAMPLE V A solution of trimethyl borate was prepared by stirring together 128.0 p.b.v. of methanol and 14.5 p.b.w. of boric acid until dissolved. Subsequently 400 p.b.v. of a 10.8%

by weight solution of calcium naphthenate in xylene and 143 p.b.v. of xylene were added to the solution- To hydrolyze the trimethyl borate a mixture of 6.3 p.b.v. of water and 100 p.b.v. of methanol was added, after which the methanol was distilled ofi. In this way 270 p.b.w. of a clear orange dispersion of boric acid in xylene, having a boric acid content of 3.5% by weight were obtained. The ratio of boric acid to calcium naphthenate in the finished product was about 0.25: 1.0 by Weight.

EXAMPLE VI The experiment shown in Example I is repeated, substituting for the calcium naphthenate, an equivalent amount of the calcium salts of C -C alkyl salicylic acids with an acid value of 86 milligrams of KOH/ gram. The product contains approximately the same concentration of boric acid as was obtained in the product of the experiment reported in Example '1.

EXAMPLE VII Lead naphthenate was prepared from naphthenic acid by first forming a sodium salt and then exchanging metathetically with lead acetate solution. A solution of trimethyl borate was prepared by dissolving 14.55 p.b.w. of boric acid in 129 p.b.v. of methanol at a temperature of C. and the lead naphthenate was added in the form of 72% solution in 67 p.b.w. of xylene. 'Ihe trimethyl borate was hydrolyzed by adding 6.3 p.b.v. of water in 100 p.b.v. of methanol, after which the methanol was removed by distillation. 288 p.b.w. of a clear dispersion of boric acid containing 1.7% by Weight of boric acid and 3.8% by weight of lead was obtained.

EXAMPLE V111 200 p.v.w. of a solution of a basic calcium naphthasulphonate in a H.V.I. oil having a viscosity of 65 sec. Redwood I at 140 F. (alkalinity 21 mg. KOH/g. sulphated ash 9.0% by weight and ca. 2.5% by weight) was stirred for 15 minutes with 29 p.b.w. of lime and 300 p.b.w. of xylene. A solution of trimethyl borate was prepared by dissolving 24 p.b.w. of boric acid in 150 p.b.w. of methanol and this solution was added dropwise to the xylene solution with continuous stirring for two hours at C. The methanol was then removed by distillation, the residue filtered and the xylene removed under high vacuum (0.1 mm. of mercury) to give a clear and bright oil which contained 1.46% by weight of boron present as calcium borate.

EXAMPLE IX Again, a product containing approximately the same content of boric acid as the product of Example V is prepared by substituting for the calcium naphthenate an equivalent amount of a trade product containing 18.5% by weight of Octylformol, the calcium salt of the condensation product of p-octylphenol with formaldehyde, said salt having a molecular weight of approximately 1000, dissolved in mineral oil.

EXAMPLE X A solution of trimethyl borate was prepared by stirring together 6.2 p.b.w. of boric acid and 43.5 p.b.w. of methanol. This solution was then added dropwise to a solution of calcium naphthenate (3.1 p.b.w.) dissolved in 198 p.b.w. of xylene. After stirring for 15 minutes at room temperature a mixture of 2.7 p.b.w. of water in 34 p.b.w. of methanol was added rapidly and the reaction mixture stirred vigorously for 10 minutes. The methanol, water, and some xylene were then removed as rapidly as possible by distillation at a pressure of 35 mm. of mercury, heating carefully by means of an oil bath the temperature of which wasnot allowed to exceed 120 C. The product was filtered cold to give a clear brown liquid (70 p.b.w.) which contained 4.0% by weight of boric acid. The storage stability of the product was tested by frequent visual examination over along period of time,

and .it was found to be perfectly stable under both open and closed conditions for more than 96 days.

EXAMPLE XI A series of preparations were conducted using various lower aliphatic alcohols as the water-miscible solvent, and in each case employing the corresponding trialkyl borate. The general method followed in these preparations was as follows:

A solution of the trialkyl borate in the alcohol was prepared by adding boric acid (0.1 mole) to the alcohol (1.4 moles) and stirring until dissolved, Warming slightly if necessary. A solution of calcium naphthenate (24.8 p.b.w.) in xylene (230 p.b.w.) was then added to the solution of trialkyl borate followed by the addition with vigorous stirring of a mixture of 2.7 p.b.v. of distilled water in 43 p.b.v. of the same alcohol that had been used to form trialkyl borate. The alcohol, water and some xylene were then removed as rapidly as possible by distillation at a pressure of 100 mm. of mercury, heating carefully by means of an oil bath. As far as possible identical Stripping conditions were employed in each of the preparations using the various alcohols. The product was then filtered hot to give a clear brown liquid which was then analyzed. The results of these preparations are shown in Table I Table I Boron/OaN Ratio Product Alcohol Mixed Percent Reaetants Product p.b.w Boric Acid These results showed that higher boron utilization was obtainable if propanol or butanol was used as the watermiscible oxygen-containing solvent in conjunction with the corresponding trialkyl borate.

EXAMPLE XII A solution of neutral calcium naphthenate in isooctane was prepared by stirn'ng a mixture of 159 p.b.w. of naphthenic acid, 348 p.b.w. methanol, 1496 p.b.w. of iso-octane together with 8 equivalents of lime for 20 hours. The product was filtered through Clarcel until clear and a small quantity of the iso-octane was removed by distillation in vacuo to give a clear strawcolored liquid containing 12% by weight of calcium naphthenate. A solution of tri-isopropyl borate was then prepared by adding 6.2 p.b.w. of boric acid to 84 p.b.w. of isopropyl alcohol and stirring until dissolved. 205 p.b.w. of the iso-octane solution of calcium naphthenate (i.e., containing 24.8 p.b.w. of calcium naphthenate) was dilutedrwith a further p.b.w. of iso-octane and was added to the solution of tii-isopropyl borate followed by the addition with vigorous stlrring of a mixture of 2.7 p.b.v. of distilled water and 43 p.b.v. of isopropyl alcohol. The alcohol, water and some xylene were then removed as rapidly as possible by distillation at atmospheric pressure the maximum temperature of the heating bath being 100 C. and the product filtered through Clarcel to give a clear liquid (90 p.b.w.) containing 0.2% boric acid.

The novel compositions provided by this invention are useful as additives to fuel compositions, particularly gasoline compositions, for use in spark-ignited internal combustion motors, especially high compression automobile and airplane motors. In such fuel compositions, the added. novel compositions act to reduce the amount and the etfect of deposits in the combustion chambers of motors in which the fuel compositions are used, thus reducing the effects of those deposits which lead to increased fuel octane number requirement and to abnormal ignition of the fuel (preignition, autoignition, wild ping, rumble, etc). The compositions of the invention may be used as the sole additive in a given fuel composition, or the fuel composition may contain other conventional additives, including known oxidation inhibitors, such as 2,6-ditertiary butyl-4-methyl phenol and N,N-di-secondary butyl-p-phenylene diamine, tetraethyl lead as antiknock agent, scavengers, such as ethylene di: bromide, and the like. The fuels containing the new compositions are conveniently prepared directly via the process of the invention, as hereinbefore described. The concentration of the added composition which ordinarily is effective for the desired purposes is that which provides at least 0.05 gram of boron per US. gallon of fuel composition. However, in many cases, some benefits are realized when the amount of additive provides but 0.005 gram of boron per US. gallon. It is normally undesirable that more than about 1.0 gram of boron per gallon of fuel be added via the additive. A preferred concentration of additive is that which supplied from about 0.2 gram to about 0.4 gram of hero per US. gallon of fuel.

The compositions of the invention also are useful mild extremepressure agents for lubricating oils and greases, as anti-oxidants, and as lubricating oil detergents. In general, the new compositions will be used in lubricating oils in concentrations between about 0.1 and 15% by weight. If desired, the salts may be combined with other additives, for instance, viscosity improvers, or the like.

We claim as our invention:

l. A process for preparing an inorganic boric acid material stably dispersible in liquid fuels and lubricant stocks, said process comprising mixing (a) a solution of a lyophilic ionic surface-active agent in a substantially non-polar organic liquid, (b) an hydrolyzable ester of boric acid, in the proportion of at least about 0.1 part by weight of said ester per part by Weight of said surfaceactive agent, and (c) a polar, non-acidic organic liquid, the amount of said polar liquid being at least about 5% of the combined weights of said polar liquid and said non-polar liquid, thereafter hydrolyzing said ester of boric acid, and thereafter recovering from the resulting reaction mixture a dispersion, in said non-polar organic liquid, of the inorganic boric acid compound resulting from the hydrolysis of said ester of boric acid.

2. A process for preparing an inorganic boric acid material stably dispersible in liquid fuels and lubricant stocks, said process comprising mixing (a) a solution of a lyophilic ionic surface-active agent in a substantially non-polar organic liquid, (b) an hydrolyzable ester of boric acid, in the proportion of at least about 0.1 part by weight of said ester per part by weight of said surfaceactive agent, and (c) a polar non-acidic organic liquid, the amount of said polar organic liquid being at least about 5% of the combined weights of said polar liquid and said non-polar liquid, thereafter hydrolyzing said ester of boric acid, and thereafter recovering from the resulting reaction mixture a dispersion, in said non-polar Organic liquid, of the inorganic boric acid compound resulting from the hydrolysis of said ester of boric acid.

3. A process according to claim 2 wherein the said surface-active agent is a lyophilic anionic surface-active agent. 7

4. A process according to claim 2 wherein the said surface-active agent is a lyophilic cationic surface-active agent.

. 5. A process for preparing an inorganic boric acid material stably dispersible in liquid fuels and lubricant stocks, said process comprising mixing (ii) a solution of a,,lyophilic ionicv surface-active agent in a substantially non-polar organic liquid, (b) an hydrolyzable ester of boric acid and an alcohol boiling below the boiling temperature of said non-polar organic liquid, in the proportion of at least about 0.1 part by weight of said ester per part by weight'of said surface-active agent, and (c) a polar non-acidic organic liquid boiling ata' temperature below the boiling temperature of said non-polar organic liquid, the amount of said polar organic liquid being at least about 5% of the combined weights of said polar liquid and said non-polar liquid, thereafter hydrolyzing said ester of boric acid, thereafter removing by vaporization the material in the resulting mixture boiling at a temperature below the boiling temperature of the said non-polar organic liquid, and thereafter recovering from the residue a dispersion in said non-polar organic liquid of the inorganic boric acid compound resulting from hydrolysis of said ester of boric acid.

6. A process according to claim 5 wherein the hydrolysis of the boric acid ester is accomplished by means of water and the inorganic boric acid compound in the product is boric acid.

7. A process according to claim 5 wherein the hydrolysis of the boric acid ester is accomplished by means of a metal base and the inorganic boric acid compound in the product is a metal borate corresponding to the said metal base.

8. A process according to claim 5 wherein the said polar organic liquid is an alcohol and wherein the said boric acid ester is found in situ by the reaction of boric acid and the alcohol used as the polar liquid.

9. A process for preparing an inorganic boric acid material stably dispersible in liquid fuels and lubricant stocks, said process comprising mixing (a) a solution of at least one salt of an organic acid containing at least 8 carbon atoms per molecule in a substantially non-polar organic liquid, (b) an hydrolyzable ester of boric acid and an alcohol boiling below the boiling temperature of said non-polar organic liquid, in the proportion of at least about 0.1 part by weight of said ester per part by weight of said salt, and (c) a polar non-acidic organic liquid boiling at a temperature below the boiling temperature of said non-polar organic liquid, the amount of said polar organic liquid being at least about 5% of the combined weights of said polar liquid and said non-polar liquid, thereafter hydrolyzing said ester of boric acid, thereafter removing by vaporization the material in the resulting mixture boiling at a temperature below the boiling temperature of the said non-polar organic liquid, and thereafter recovering from the residue a dispersion in said non-polar organic liquid of the inorganic boric acid compound resulting from hydrolysis of said ester of boric acid.

10. A process for preparing an inorganic boric acid material stably dispersible in liquid fuels and lubricant stocks, said process comprising mixing (a) a solution of at least one oil-soluble'salt of a phenolic compound, containing at least 8 carbon atoms 'per molecule in' a substantially non-polar organic liquid, (b) an hydrolyzable ester of boric acid and an alcohol boiling below the boiling temperature of said non-polar organic liquid, in the proportion of at least about 0.1 part by'weight of said ester'per part by weight of said salt, and (c) a polar non-acidic organic liquid boiling at a temperature below the boiling temperature of said non-polar organic liquid, the amount of said polar organic liquid being at least about 5% of the combined weights ,of said polar liquid and said non-polar liquid, thereafter hydrolyzing said ester of boric acid, thereafter removing by vaporization the material in the resulting mixture boiling at a temperature below the boiling temperature of the said non-polar organic liquid, and thereafter recovering fromthe residue a dispersion in said non-polar organic liquid of the inorganic boric acid compound resulting from hydrolysis of said ester of boric acid.

ll. A process for preparing an inorganic boric acid material stably dispersible in liquid fuels and lubricant stocks, said process comprising mixing (a) a solution of at least one oil-soluble organic amino compound containing at least 8 carbon atoms per molecule in a substantially non-polar organic liquid, (b) an hydrolyzable ester of boric acid and an alcohol boiling below the boiling temperature of said non-polar organic liquid, in the proportion of at least about 0.1 part by weight of said ester per part by weight of said amino compound, and (c) a polar non-acidic organic liquid boiling at a temperature below the boiling temperature of said nonpolar organic liquid, the amount of said polar organic liquid being at least about of the combined weights of said polar liquid and said non-polar liquid, thereafter hydrolyzing said ester of boric acid, thereafter removing by vaporization the material in the resulting mixture boiling at a temperature below the boiling temperature of the said non-polar organic liquid, and thereafter recovering from the residue a dispersion in said non-polar organic liquid of the inorganic boric acid compound resulting from hydrolysis of said ester of boric acid.

12. A process for preparing an inorganic boric acid material stably dispersible in liquid fuels and lubricant stocks, said process comprising mixing (a) a solution of at least one oil-soluble alkaline earth metal salt of an alkyl-substituted aromatic hydroxy carboxylic acid in a liquid hydrocarbon, (b) an hydrolyzable ester of boric acid and an alkanol boiling at a temperature below the boiling temperature of the liquid hydrocarbon, in the proportion of from about 0.1 to about 1 part by weight of said ester per part by weight of said salt, and (c) a lower aliphatic alcohol, the amount of said alcohol being at least about 5% of the combined weights of said liquid hydrocarbon and said alcohol, thereafter hydrolyzing said ester of boric acid, thereafter removing by vaporization the material in the resulting mixture boiling at a temperature below the boiling temperature of the said liquid hydrocarbon, and thereafter recovering from the residue a dispersion in said liquid hydrocarbon of the inorganic boric acid compound resulting from hydrolysis of said ester of boric acid.

13. A process for preparing an inorganic boric acid material stably dispersible in liquid fuels and lubricant stocks, said process comprising mixing (a) a solution of at least one oil-soluble alkaline earth metal salt of a petroleum sulfonic acid in a liquid hydrocarbon, (b) an hydrolyzable ester of boric acid and an alkanol boiling at a temperature below the boiling temperature of the liquid hydrocarbon, in the proportion of from about 0.1 to about 1 part by weight of said ester per part by weight of said salt, and (c) a lower aliphatic alcohol, the amount of said alcohol being at least about 5% of the combined weights of said liquid hydrocarbon and said alcohol, thereafter hydrolyzing said ester of boric acid, thereafter removing by vaporization the material in the resulting mixture boiling at a temperature below the boiling temperature of the said liquid hydrocarbon, and thereafter recovering from the residue a dispersion in said liquid hydrocarbon of the inorganic boric acid compound resulting from hydrolysis of said ester of boric acid.

14. A process for preparing an inorganic boric acid material stably dispersible in liquid fuels and lubricant stocks, said process comprising mixing (a) a solution of at least one oil-soluble alkaline earth metal salt of a petroleum naphthenic acid in a liquid hydrocarbon, (b) an hydrolyzable ester of boric acid and an alkanol boiling at a temperature below the boiling temperature of the liquid hydrocarbon, in the proportion of from about 0.1 to about 1 part by weight of said ester per part by weight of said salt, and (c) a lower aliphatic alcohol, the amount of said alcohol being at least about 5% of the combined weights of said liquid hydrocarbon and said alcohol, thereafter hydrolyzing said ester of boric acid, thereafter removing by vaporization the material in the resulting mixture boiling at a temperature below the boiling temperature of the said liquid hydrocarbon, and thereafter recovering from the residue a dispersion in said liquid hydrocarbon of the inorganic boric acid compound resulting from hydrolysis of said ester of boric acid.

15. A process for preparing an inorganic boric acid material stably dispersible in liquid fuels and lubricant stocks, said process comprising mixing (a) a solution of at least one oil-soluble alkaline earth metal salt of a condensation product of an oil-soluble phenol with a low molecular weight carbonylic compound in a liquid hydrocarbon, (b) an hydrolyzable ester of boric acid and an alkanol boiling at a temperature below the boiling temperature of the liquid hydrocarbon, in the proportion of from about 0.1 to about '1 part by weight of said ester per part by weight of said salt, and (c) a lower aliphatic alcohol, the amount of said alcohol being at least about 5% of the combined weights of said liquid hydrocarbon and said alcohol, thereafter hydrolyzing said ester of boric acid, thereafter removing by vaporization the material in the resulting mixture boiling at a temperature below the boiling temperature of the said liquid hydrocarbon, and thereafter recovering from the residue a dispersion in said liquid hydrocarbon of the inorganic boric acid compound resulting from hydrolysis of said ester of boric acid.

16. A process for preparing an inorganic boric acid material stably dispersible in liquid fuels and lubricant stocks, said process comprising mixing (a) a solution of at least one long chain aliphatic amine in a liquid hydrocarbon, (b) an hydrolyzable ester of boric acid and an alkanol boiling at a temperature below the boiling temperature of the liquid hydrocarbon, in the proportion of from about 0.1 to about 1 part by weight of said ester per part by weight of said salt, and (c) a lower aliphatic alcohol, the amount of said alcohol being at least about 5% of the combined weights of said liquid hydrocarbon and said alcohol, thereafter hydrolyzing said ester of boric acid, thereafter removing by vaporization the material in the resulting mixture boiling at a temperature below the boiling temperature of the said liquid hydrocarbon, and thereafter recovering from the residue a dispersion in said liquid hydrocarbon of the inorganic boric acid compound resulting from hydrolysis of said ester of boric acid.

References Cited in the file of this patent UNITED STATES PATENTS 2,312,208 Olayton et a1. Feb. 23, 1943 2,614,985 Cook Oct. 21, 1952 2,710,252 Darling June 7, 1955 2,749,310 Williams et a1. June 5, 1956 2,815,325 Pohorilla et al. Dec. 3, 1957 2,866,811 Irish et a1. Dec. 30, 1958 2,875,236 Levens et a1. Feb. 24, 1959 FOREIGN PATENTS 540,192 Canada Apr. 30, 1957 

1. A PROCESS FOR PREPARING AN INORGANIC BORIC ACID MATERIAL STABLY DISPERSIBLE IN LIQUID FUELS AND LUBRICANT STOCKS, SAID PROCESS COMPRISING MIXING (A) A SOLUTION OF A LYOPHILIC IONIC SURFACE-ACTIVE AGENT IN A SUBSTANTIALLY NON-POLAR ORGANIC LIQUID, (B) AN HYDROLYZABLE ESTER OF BORIC ACID, IN THE PROPORTION OF AT LEAST ABOUT 0.1 PART BY WEIGHT OF SAID ESTER PER PART BY WEIGHT OF SAID SURFACEACTIVE AGENT, AND (C) A POLAR, NON-ACIDIC ORGANIC LIQUID, THE AMOUNT OF SAID POLAR LIQUID BEING AT LEAST ABOUT 5% OF THE COMBINED WEIGHTS OF SAID POLAR LIQUID AND SAID NON-POLAR LIQUID, THEREAFTER HYDROLYZING SAID ESTER OF BORIC ACID, AND THEREAFTER RECOVERING FROM THE RESULTING REACTION MIXTURE A DISPERSION, IN SAID NON-POLAR ORGANIC LIQUID, OF THE INORGANIC BORIC ACID COMPOUND RESULTING FROM THE HYDROLYSIS OF SAID ESTER OF BORIC ACID. 